CN111040356B - Three-primary-color photoluminescence device and preparation method thereof - Google Patents
Three-primary-color photoluminescence device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a three-primary-color photoluminescence device and a preparation method thereof, comprising the following steps: firstly, preparing a solution of europium chloride, terbium chloride and zinc chloride, and synthesizing an amphiphilic block polymer through RAFT polymerization to prepare a polymer solution. Then, the amphiphilic block polymer, a small molecule ligand phenanthroline (Phen), 2-Thenoyl Trifluoroacetone (TTA) acetylacetone (acac), salicylic acid, imidazole (Im) and Benzothiazole (BTZ) are coordinated and complexed with metal ions. Polyacrylic acid (PAA) segments, phen, TTA, acac, salicylic acid, im and BTZ form a network structure with metal ions, while polystyrene PS segments can be dispersed in N, N-dimethylformamide solution. The invention has simple process, can convert ultraviolet light into visible light, and can change the color of the light-emitting device only by changing the patch.
Description
Technical Field
The invention relates to a three-primary-color photoluminescent device and a preparation method thereof, belonging to the technical field of photoluminescent device preparation.
Background
In recent years, as rare earth luminescent films have been widely used in the fields of display systems and lighting technologies, researchers have been strongly interested in rare earth luminescent films.
Ions that can be used as luminescent centers include rare earth ions and transition metal ions. Rare earth elements have very rich electron energy levels, and their unique transition properties of 4f orbital electrons enable them to have various light-emitting characteristics, such as linear emission and high light-emitting efficiency, and the spectral shape is hardly affected by temperature.
Disclosure of Invention
The invention provides a three-primary-color photoluminescence device and a preparation method thereof by utilizing metal ion-inducible polymer self-assembly.
The technical scheme of the invention is as follows:
a method of fabricating a three primary color photoluminescent device comprising the steps of:
step a: under the condition of stirring, respectively dissolving europium chloride crystals, terbium chloride crystals and zinc chloride in an N, N-Dimethylformamide (DMF) solvent to respectively prepare europium chloride solution, terbium chloride solution and zinc chloride solution with certain concentration;
step b: preparing an amphiphilic block polymer PS-b-PAA by a RAFT polymerization method;
step c: under the condition of stirring, dissolving the amphiphilic block polymer PS-b-PAA prepared in the step b in a proper amount of DMF solvent to prepare a polymer solution with a certain concentration;
step d: under the stirring condition, taking the organic ligand Phen or TTA, the polymer solution prepared in the step c and the europium chloride solution prepared in the step a, adding the three into a beaker according to the proportion of 1:2:1, adjusting the PH to be 5-6, heating at 50-70 ℃ for 5-8 hours, and obtaining liquid which is the polymer-europium nanoparticle solution capable of emitting red light;
step e: under the stirring condition, taking an organic ligand acac or salicylic acid, adding the polymer solution prepared in the step c and the terbium chloride solution prepared in the step a into a beaker according to the ratio of 1:2:1, adjusting the PH to be 5-6, heating at 50-70 ℃ for 5-8 hours, and obtaining liquid which is the polymer-terbium nanoparticle solution capable of emitting green light;
step f: under the stirring condition, taking the polymer solution prepared in the organic ligand Im or BTZ, c and the zinc chloride solution prepared in the step a, adding the three into a beaker according to the proportion of 1:2:1, adjusting the PH to be 5-6, heating at 50-70 ℃ for 5-8 hours, and obtaining liquid which is the polymer-zinc nanoparticle solution capable of emitting blue light;
step g: dissolving a proper amount of PAN in a certain amount of DMF solution to prepare DMF solution with the mass fraction of PAN of 10%;
step h: mixing the luminescent nanoparticle solutions prepared in the steps e, f and g with a certain amount of PAN solution respectively to obtain three uniform mixed solutions;
step i: pouring the three uniform mixed solutions obtained in the step h on a glass plate with a flat surface, putting the glass plate into a baking oven with the temperature of 40-60 ℃ for 24 hours, and drying the glass plate, wherein the lifted transparent film is the luminous film;
step j: and (3) taking the three films prepared in the step (i) as luminous patches of the LED lamp, namely preparing the photoluminescence devices of three primary colors of red, green and blue by using a single LED lamp.
The preparation method of the amphiphilic block polymer PS-b-PAA comprises the following steps: (1) Adding a proper amount of chain transfer agent (RAFT) and a certain amount of initiator azodiisobutyronitrile into a container, adding a proper amount of dioxane solvent to fully dissolve the initiator azodiisobutyronitrile, adding a proper amount of styrene monomer, rapidly sealing, and uniformly stirring the mixed solution; introducing nitrogen for 30-50 minutes to completely exhaust the air in the container; heating at 70-90 ℃ for polymerization for 9-11 hours under the atmosphere of nitrogen; after polymerization is completed, a small amount of tetrahydrofuran is added, and stirring and dissolution are carried out; after dissolution, dropwise dripping the mixture into excessive methanol solution under the stirring condition, and generating yellow solid; filtering the mixed solution, repeatedly washing for three times to obtain yellow solid, and drying in a 50 ℃ oven for 24 hours to obtain Polystyrene (PS) powder; (2) Adding a certain amount of initiator azodiisobutyronitrile and PS powder in the step (1) into another container, adding a proper amount of dioxane solvent to fully dissolve the initiator azodiisobutyronitrile and PS powder, adding a proper amount of acrylic acid monomer, and sealing; stirring the mixed solution uniformly; introducing nitrogen for 30-50 minutes to completely exhaust the air in the container; heating at 60-70 ℃ for polymerization for 9-11 hours under the atmosphere of nitrogen; after polymerization is completed, a small amount of tetrahydrofuran is added, and stirring and dissolution are carried out; after dissolution, dropwise adding the mixture into excessive petroleum ether solution under stirring, wherein yellow solid is generated; and (3) carrying out suction filtration on the mixed solution, repeatedly washing for three times to obtain yellow solid, and putting the yellow solid into a 50 ℃ oven for drying for 24 hours to finally obtain the amphiphilic block polymer PS-b-PAA solid.
According to the preparation method, the stirring speed in the step a is 200-300 r/min, the stirring speed in the step c is 200-500 r/min, and the stirring speeds in the steps d, e and f are 400-600 r/min.
In the preparation method, the concentration of europium chloride, terbium chloride and zinc chloride in the step a is 1.0-4.0X10-2 mol/L.
In the preparation method, the concentration of the amphiphilic block polymer in the step c is 1.0-4.0X10-2 mol/L.
The preparation method comprises the steps of preparing a polymer-europium nanoparticle solution:
(1) Adding 5mL of N, N-dimethylformamide solution serving as a solvent into a round-bottom flask under the stirring condition of 300 r/min;
(2) Adding 0.15g of organic ligand phenanthroline into the N, N-dimethylformamide solution stirred in the step (1), continuously stirring for 30min to completely dissolve the phenanthroline, and uniformly mixing the solution;
(3) Adding 10mL of amphiphilic block polymer solution with the concentration of 0.1mol/L into the uniformly stirred phenanthroline solution, and continuously stirring for 30min to uniformly mix the solutions;
(4) Slowly dropwise adding 5mL of europium chloride solution with the concentration of 0.1mol/L into the mixed solution obtained in the step (3) under the stirring condition, and uniformly mixing to obtain a colorless transparent solution.
The preparation method comprises the steps of preparing a polymer-terbium nanoparticle solution:
(1) Adding 5mL of N, N-dimethylformamide solution serving as a solvent into a round-bottom flask under the stirring condition of 300 r/min;
(2) Adding 0.21g of an organic ligand acac into the N, N-dimethylformamide solution stirred in the step (1), continuously stirring for 30min to completely dissolve the acac, and uniformly mixing the solution;
(3) Adding 10mL of amphiphilic block polymer solution with the concentration of 0.1mol/L into the uniformly stirred acac solution, and continuously stirring for 30min to uniformly mix the solution;
(4) Slowly dropwise adding 5mL terbium chloride solution with the concentration of 0.1mol/L into the mixed solution under the stirring condition, and uniformly mixing to obtain colorless transparent solution;
(5) Placing the obtained colorless transparent mixed solution into an oil bath pot at 60 ℃ for heating reaction for 7 hours; after the reaction is finished, colorless transparent solution is obtained, namely the polymer-terbium nanoparticle solution.
The preparation method comprises the steps of preparing a polymer-zinc nanoparticle solution:
(1) Adding 5mL of N, N-dimethylformamide solution serving as a solvent into a round-bottom flask under the stirring condition of 300 r/min;
(2) Adding 0.23g of organic ligand Im into the stirred N, N-dimethylformamide solution, continuously stirring for 30min to completely dissolve the Im, and uniformly mixing the solution;
(3) Adding 10mL of amphiphilic block polymer solution with the concentration of 0.1mol/L into the uniformly stirred Im solution, and continuously stirring for 30min to uniformly mix the solution;
(4) Slowly dropwise adding 5mL of zinc chloride solution with the concentration of 0.1mol/L into the mixed solution under the stirring condition, and uniformly mixing to obtain a colorless transparent solution;
(5) Placing the obtained colorless transparent mixed solution into an oil bath pot at 60 ℃ for heating reaction for 7 hours; after the reaction is finished, colorless transparent solution is obtained, namely the polymer-zinc nanoparticle solution.
According to the preparation method, the LED lamp is an ultraviolet LED lamp with the wavelength of 365 nm.
A trichromatic photoluminescent device prepared according to any one of the preparation methods.
Compared with the prior art, the invention has the following advantages:
the invention uses Phen, TTA, acac, salicylic acid, im and BTZ as organic ligand and Eu respectively 3+ 、Tb 3+ And Zn 2+ The ions are coordinated and added into the solution of the amphiphilic block polymer PS-b-PAA to induce the block polymer to self-assemble, so as to prepare metal nano particles, and then the metal nano particles are doped with PAN to prepare the luminescent film capable of respectively emitting three primary colors of red, green and blue. The fluorescent powder of the LED is mainly inorganic rare earth, and has complex preparation process and reactionThe invention changes the series of problems by utilizing the amphiphilic block polymer, and the self-assembly of the block polymer ensures that the nano particles are uniformly dispersed, so that the luminous film is uniform. The film can be used as an LED luminous patch to prepare a photoluminescence device. All three luminescent films can be excited by 365nm ultraviolet light. Thus, only one LED can be used as a light source, and the light-emitting color of the LED can be changed by changing the light-emitting film. Meanwhile, the polymer has flexibility and can be used for preparing a light source which is easy to fold and carry, but the application of the polymer in the aspect of light emission is limited due to the non-conductivity of the polymer. The photoluminescent device solves the problem, so that the polymer is applied in the field, and the excellent performance of the polymer and the luminescent performance of metal ions are combined together.
Drawings
FIG. 1 is a solid state fluorescence of the Eu/PAN film prepared;
FIG. 2 is the solid state fluorescence of the Tb/PAN film prepared;
FIG. 3 is the solid state fluorescence of the Tb/PAN film prepared;
FIG. 4 is a chromaticity diagram of luminescence of Eu/PAN film, tb/PAN film and Zn/PAN film, and colors of the luminescence correspond to a, b and c in the diagram, respectively.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Europium chloride in the examples was purchased from Shanghai dary Fine chemical Co., ltd;
terbium chloride was purchased from Shanghai Darui Fine chemical Co., ltd;
zinc chloride was purchased from Shanghai dary fine chemicals limited;
1, 10-phenanthroline was purchased from red rock reagent factories in Tianjin;
2-thenoyltrifluoroacetone (TTA), acetylacetone (acac), salicylic acid, imidazole (Im) and Benzothiazole (BTZ)
Purchased from aladine;
n, N-dimethylformamide was purchased from Tianjin Fuyu chemical Co., ltd;
the fluorescence emission spectrum of the sample prepared by the invention is obtained by detection of a American Cary Eclipse fluorescence spectrophotometer.
Example 1: preparation of amphiphilic Block Polymer polystyrene-b-polyacrylic acid (PS-b-PAA).
(1) Preparation of first block polystyrene PS: in a 50mL round bottom flask, 0.177g of chain transfer agent (RAFT) and 0.027g of initiator azobisisobutyronitrile were added, and 4mL of dioxane solvent was added to dissolve it sufficiently, and then 1.04g of styrene monomer was added, and the rubber stopper was quickly plugged, and the bottle mouth was completely sealed with a sealing film. And stirring the mixed solution uniformly. Nitrogen was purged for 40 minutes to allow the air in the round bottom flask to completely purge. The polymerization was carried out by heating at 90℃for 11 hours while maintaining a nitrogen atmosphere. After the polymerization is completed, a small amount of tetrahydrofuran is added and stirred for dissolution. After dissolution, a yellow solid was produced by dropwise dropping into an excessive amount of methanol solution with stirring. And filtering the mixed solution, repeatedly washing for three times to obtain yellow solid, and drying the yellow solid in a 50 ℃ oven for 24 hours to obtain Polystyrene (PS) powder.
(2) In a 50mL round bottom flask, 0.034g of initiator azobisisobutyronitrile and 1g of PS powder prepared in step (1) were added, and sufficiently dissolved by adding 5mL of dioxane solvent, and then 0.422g of acrylic acid monomer were added, and a rubber stopper was quickly plugged, and the bottle mouth was completely sealed with a sealing film. And stirring the mixed solution uniformly. Nitrogen was purged for 40 minutes to allow the air in the round bottom flask to completely purge. The polymerization was carried out by heating at 70℃for 11 hours while maintaining a nitrogen atmosphere. After the polymerization is completed, a small amount of tetrahydrofuran is added and stirred for dissolution. After dissolution, a yellow solid was produced by dropwise dropping into an excess of petroleum ether solution with stirring. And (3) carrying out suction filtration on the mixed solution, repeatedly washing for three times to obtain yellow solid, and putting the yellow solid into a 50 ℃ oven for drying for 24 hours to finally obtain the amphiphilic block polymer PS-b-PAA solid.
Example 2 preparation of Polymer and Metal ion solution
(1) Preparation of europium chloride solution: 1.832g EuCl was weighed out 3 ·6H 2 O, with small amounts of N, N-dimethylAnd (3) completely dissolving europium chloride by using the dimethylformamide, transferring the solution into a 50mL volumetric flask, diluting the solution to a scale by using N, N-dimethylformamide, and uniformly mixing the solution to prepare 0.1mol/L europium chloride solution for later use.
(2) Preparation of terbium chloride solution: 1.868g TbCl was weighed out 3 ·6H 2 And (3) completely dissolving terbium chloride by using a small amount of N, N-dimethylformamide, transferring to a 50mL volumetric flask, diluting to a scale by using the N, N-dimethylformamide, and uniformly mixing to prepare a terbium chloride solution with the concentration of 0.1mol/L for later use.
(3) Preparation of zinc chloride solution: weighing 0.682g ZnCl 2 The zinc chloride is completely dissolved by using a small amount of N, N-dimethylformamide, transferred into a 50mL volumetric flask, diluted to a scale by using the N, N-dimethylformamide, and uniformly mixed to prepare a zinc chloride solution with the concentration of 0.1mol/L for later use.
(4) Preparation of amphiphilic block polymer solution: under the condition of stirring, N-dimethylformamide is used as a solvent to respectively dissolve the amphiphilic block polymer PS-b-PAA, so as to prepare the amphiphilic block polymer solution with the concentration of 0.1 mol/L.
Example 4: preparation of Polymer-europium nanoparticle solutions
(1) 5mL of N, N-dimethylformamide solution was added as a solvent to a round bottom flask with stirring at 300 r/min.
(2) Adding 0.15g of organic ligand phenanthroline into the N, N-dimethylformamide solution stirred in the step (1), continuously stirring for 30min to completely dissolve the phenanthroline, and uniformly mixing the solution;
(3) Adding 10mL of amphiphilic block polymer solution with the concentration of 0.1mol/L into the uniformly stirred phenanthroline solution, and continuously stirring for 30min to uniformly mix the solutions;
(4) Slowly dropwise adding 5mL of europium chloride solution with the concentration of 0.1mol/L into the mixed solution obtained in the step (3) under the stirring condition, and uniformly mixing to obtain a colorless transparent solution.
(5) The obtained colorless transparent mixed solution was placed in an oil bath at 60℃and heated to react for 7 hours. And after the reaction is finished, obtaining colorless transparent solution, namely polymer-europium nanoparticle solution.
Example 5: preparation of Polymer-terbium nanoparticle solutions
(1) 5mL of N, N-dimethylformamide solution was added as a solvent to a round bottom flask with stirring at 300 r/min.
(2) Adding 0.21g of an organic ligand acac into the N, N-dimethylformamide solution stirred in the step (1), continuously stirring for 30min to completely dissolve the acac, and uniformly mixing the solution;
(3) Adding 10mL of amphiphilic block polymer solution with the concentration of 0.1mol/L into the uniformly stirred acac solution, and continuously stirring for 30min to uniformly mix the solution;
(4) Slowly and dropwise adding 5mL of terbium chloride solution with the concentration of 0.1mol/L into the mixed solution under the stirring condition, and uniformly mixing to obtain a colorless transparent solution.
(5) The obtained colorless transparent mixed solution was placed in an oil bath at 60℃and heated to react for 7 hours. After the reaction is finished, colorless transparent solution is obtained, namely the polymer-terbium nanoparticle solution.
Example 6: preparation of Polymer-Zinc nanoparticle solutions
(1) 5mL of N, N-dimethylformamide solution was added as a solvent to a round bottom flask with stirring at 300 r/min.
(2) Adding 0.23g of organic ligand Im into the stirred N, N-dimethylformamide solution, continuously stirring for 30min to completely dissolve the Im, and uniformly mixing the solution;
(3) Adding 10mL of amphiphilic block polymer solution with the concentration of 0.1mol/L into the uniformly stirred Im solution, and continuously stirring for 30min to uniformly mix the solution;
(4) Slowly and dropwise adding 5mL of zinc chloride solution with the concentration of 0.1mol/L into the mixed solution under the stirring condition, and uniformly mixing to obtain a colorless transparent solution.
(5) The obtained colorless transparent mixed solution was placed in an oil bath at 60℃and heated to react for 7 hours. After the reaction is finished, colorless transparent solution is obtained, namely the polymer-zinc nanoparticle solution.
Example 7: preparation of Polymer-Metal luminescent film
(1) 27g of DMF solvent is added into a beaker, 3g of PAN solid is weighed, added into the beaker, stirred, and sealed for standby after PAN is completely dissolved.
(2) 2mL of PAN solution prepared in the step (1) is added into a small beaker, 3mL of polymer-europium nanoparticle solution with the concentration of 0.1mol/L is added, the mixture is uniformly mixed with the PAN solution, the mixed solution is poured onto a glass sheet with a smooth and flat surface, the glass sheet is placed into a baking oven at 60 ℃ for 24 hours, and after the glass sheet is completely dried, the film can be directly removed from the glass sheet.
(3) 2mL of PAN solution is added into a small beaker, 3mL of polymer-terbium nanoparticle solution with the concentration of 0.1mol/L is added, the mixture is uniformly mixed with the PAN solution, the mixed solution is poured onto a glass sheet with a smooth and flat surface, the glass sheet is placed into a baking oven with the temperature of 60 ℃ for 24 hours, and after the glass sheet is completely dried, the film can be directly removed from the glass sheet.
(4) 2mL of PAN solution is added into a small beaker, 3mL of polymer-zinc nanoparticle solution with the concentration of 0.1mol/L is added, the mixture is uniformly mixed with the PAN solution, the mixed solution is poured onto a glass sheet with a smooth and flat surface, the glass sheet is placed into a baking oven with the temperature of 60 ℃ for 24 hours, and after the glass sheet is completely dried, the film can be directly removed from the glass sheet.
(5) And respectively taking luminescent films of europium, terbium and zinc as LED luminescent patches, and placing the luminescent patches in the same LED to prepare the photoluminescent devices of three primary colors of red, green and blue.
The polymer-metal nanoparticle prepared in example 7 was excited with 365nm LED excitation light to obtain its solid fluorescence emission spectra as shown in fig. 1,2, and 3. As can be seen from the fluorescence spectra, the emission peaks are at 615nm,545nm and 460nm, respectively, corresponding to red light, green light and blue light, respectively, and the CIE coordinates corresponding to the emission peaks are a (0.5611,0.3134), b (0.2857,0.5583) and c (0.1368,0.1538), respectively, as shown in FIG. 4.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.
Claims (10)
1. A method of manufacturing a three primary color photoluminescent device comprising the steps of:
step a: under the condition of stirring, respectively dissolving europium chloride crystals, terbium chloride crystals and zinc chloride in an N, N-Dimethylformamide (DMF) solvent to respectively prepare europium chloride solution, terbium chloride solution and zinc chloride solution with certain concentration;
step b: preparing an amphiphilic block polymer PS-b-PAA by a RAFT polymerization method;
step c: under the condition of stirring, dissolving the amphiphilic block polymer PS-b-PAA prepared in the step b in a proper amount of DMF solvent to prepare a polymer solution with a certain concentration;
step d: under the stirring condition, taking the polymer solution prepared in the step c and the europium chloride solution prepared in the step a, adding the three into a beaker according to the ratio of 1:2:1, adjusting the pH to 5-6, and heating at 50-70 ℃ for 5-8 hours to obtain liquid, namely the polymer-europium nanoparticle solution capable of emitting red light;
step e: under the stirring condition, taking an organic ligand acetylacetone acac, the polymer solution prepared in the step c and the terbium chloride solution prepared in the step a, adding the three into a beaker according to the ratio of 1:2:1, adjusting the pH to 5-6, and heating at 50-70 ℃ for 5-8 hours to obtain a liquid which is the polymer-terbium nanoparticle solution capable of emitting green light;
step f: under the stirring condition, taking the polymer solution prepared in the organic ligand imidazole Im, c and the zinc chloride solution prepared in the a, adding the three into a beaker according to the proportion of 1:2:1, adjusting the pH value to be 5-6, and heating at 50-70 ℃ for 5-8 hours, wherein the obtained liquid is the polymer-zinc nanoparticle solution capable of emitting blue light;
step g: dissolving a proper amount of PAN in a certain amount of DMF solution to prepare DMF solution with the mass fraction of PAN of 10%;
step h: d, respectively mixing the luminescent nanoparticle solutions prepared in the steps d, e and f with a certain amount of PAN solution to obtain three uniform mixed solutions;
step i: pouring the three uniform mixed solutions obtained in the step h on a glass plate with a flat surface, putting the glass plate into a baking oven with the temperature of 40-60 ℃ for 24 hours, and drying the glass plate, wherein the lifted transparent film is the luminous film;
step j: and (3) taking the three films prepared in the step (i) as luminous patches of the LED lamp, namely preparing the photoluminescence devices of three primary colors of red, green and blue by using a single LED lamp.
2. The preparation method of the amphiphilic block polymer PS-b-PAA according to claim 1, wherein the preparation method comprises the following steps: (1) Adding a proper amount of chain transfer agent and a certain amount of initiator azodiisobutyronitrile into a container, adding a proper amount of dioxane solvent to fully dissolve the initiator azodiisobutyronitrile, adding a proper amount of styrene monomer, rapidly sealing, and uniformly stirring the mixed solution; introducing nitrogen for 30-50 minutes to completely exhaust the air in the container; heating at 70-90 ℃ for polymerization for 9-11 hours under the atmosphere of nitrogen; after polymerization is completed, a small amount of tetrahydrofuran is added, and stirring and dissolution are carried out; after dissolution, dropwise dripping the mixture into excessive methanol solution under the stirring condition, and generating yellow solid; filtering the mixed solution, repeatedly washing for three times to obtain yellow solid, and drying in a 50 ℃ oven for 24 hours to obtain Polystyrene (PS) powder; (2) Adding a certain amount of initiator azodiisobutyronitrile and PS powder in the step (1) into another container, adding a proper amount of dioxane solvent to fully dissolve the initiator azodiisobutyronitrile and PS powder, adding a proper amount of acrylic acid monomer, and sealing; stirring the mixed solution uniformly; introducing nitrogen for 30-50 minutes to completely exhaust the air in the container; heating at 60-70 ℃ for polymerization for 9-11 hours under the atmosphere of nitrogen; after polymerization is completed, a small amount of tetrahydrofuran is added, and stirring and dissolution are carried out; after dissolution, dropwise adding the mixture into excessive petroleum ether solution under stirring, wherein yellow solid is generated; and (3) carrying out suction filtration on the mixed solution, repeatedly washing for three times to obtain yellow solid, and putting the yellow solid into a 50 ℃ oven for drying for 24 hours to finally obtain the amphiphilic block polymer PS-b-PAA solid.
3. The method according to claim 1, wherein the stirring rate in step a is 200-300 r/min, the stirring rate in step c is 200-500 r/min, and the stirring rates in steps d, e, and f are 400-600 r/min.
4. The method according to claim 1, wherein the europium chloride, terbium chloride and zinc chloride are present in the concentrations of 1.0 to 4.0X10% in step a -2 mol/L。
5. The method according to claim 1, wherein the concentration of the amphiphilic block polymer in step c is 1.0 to 4.0X10 -2 mol/L。
6. The method of claim 1, wherein the preparation of the polymer-europium nanoparticle solution:
(1) Adding 5mL of N, N-dimethylformamide solution serving as a solvent into a round-bottom flask under the stirring condition of 300 r/min;
(2) Adding 0.15g of organic ligand phenanthroline into the N, N-dimethylformamide solution stirred in the step (1), continuously stirring for 30min to completely dissolve the phenanthroline, and uniformly mixing the solution;
(3) Adding 10mL of amphiphilic block polymer solution with the concentration of 0.1mol/L into the uniformly stirred phenanthroline solution, and continuously stirring for 30min to uniformly mix the solutions;
(4) Slowly dropwise adding 5mL of europium chloride solution with the concentration of 0.1mol/L into the mixed solution obtained in the step (3) under the stirring condition, and uniformly mixing to obtain a colorless transparent solution.
7. The method of claim 1, wherein the preparation of the polymer-terbium nanoparticle solution:
(1) Adding 5mL of N, N-dimethylformamide solution serving as a solvent into a round-bottom flask under the stirring condition of 300 r/min;
(2) Adding 0.21g of organic ligand acetylacetone acac into the N, N-dimethylformamide solution stirred in the step (1), continuously stirring for 30min to completely dissolve the acetylacetone acac, and uniformly mixing the solution;
(3) Adding 10mL of amphiphilic block polymer solution with the concentration of 0.1mol/L into the uniformly stirred acetylacetone acac solution, and continuously stirring for 30min to uniformly mix the solutions;
(4) Slowly dropwise adding 5mL terbium chloride solution with the concentration of 0.1mol/L into the mixed solution under the stirring condition, and uniformly mixing to obtain colorless transparent solution;
(5) Placing the obtained colorless transparent mixed solution into an oil bath pot at 60 ℃ for heating reaction for 7 hours; after the reaction is finished, colorless transparent solution is obtained, namely the polymer-terbium nanoparticle solution.
8. The method of claim 1, wherein the preparation of the polymer-zinc nanoparticle solution:
(1) Adding 5mL of N, N-dimethylformamide solution serving as a solvent into a round-bottom flask under the stirring condition of 300 r/min;
(2) Adding 0.23g of organic ligand imidazole Im into the stirred N, N-dimethylformamide solution, continuously stirring for 30min to completely dissolve the imidazole Im, and uniformly mixing the solution;
(3) Adding 10mL of amphiphilic block polymer solution with the concentration of 0.1mol/L into the well-stirred imidazole Im solution, and continuously stirring for 30min to uniformly mix the solution;
(4) Slowly dropwise adding 5mL of zinc chloride solution with the concentration of 0.1mol/L into the mixed solution under the stirring condition, and uniformly mixing to obtain a colorless transparent solution;
(5) Placing the obtained colorless transparent mixed solution into an oil bath pot at 60 ℃ for heating reaction for 7 hours; after the reaction is finished, colorless transparent solution is obtained, namely the polymer-zinc nanoparticle solution.
9. The method of claim 1, wherein the LED lamp is a 365nm uv LED lamp.
10. A trichromatic photoluminescent device prepared according to the preparation method of any one of claims 1 to 9.
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